US3362983A - Process for the manufacture of ethylenes substituted in the 1-position - Google Patents
Process for the manufacture of ethylenes substituted in the 1-position Download PDFInfo
- Publication number
- US3362983A US3362983A US377413A US37741364A US3362983A US 3362983 A US3362983 A US 3362983A US 377413 A US377413 A US 377413A US 37741364 A US37741364 A US 37741364A US 3362983 A US3362983 A US 3362983A
- Authority
- US
- United States
- Prior art keywords
- cyclobutane
- cleavage
- temperature
- group
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 16
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000003776 cleavage reaction Methods 0.000 description 20
- 230000007017 scission Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 125000002560 nitrile group Chemical group 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- CVFVQKRIKMWLTJ-UHFFFAOYSA-N 1,2-dibromocyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(Br)CCC1(Br)C(O)=O CVFVQKRIKMWLTJ-UHFFFAOYSA-N 0.000 description 3
- -1 1,2-dibromocyclobutane-1,2-dinitrile Chemical compound 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- SUSAGCZZQKACKE-UHFFFAOYSA-N cyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC1C(O)=O SUSAGCZZQKACKE-UHFFFAOYSA-N 0.000 description 3
- 150000001930 cyclobutanes Chemical class 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 3
- IVAGOJQDJFWIRT-OLQVQODUSA-N (1s,2r)-1,2-dimethylcyclobutane Chemical compound C[C@H]1CC[C@H]1C IVAGOJQDJFWIRT-OLQVQODUSA-N 0.000 description 2
- MKEHNGFZTJTLBC-UHFFFAOYSA-N 1,2-dichlorocyclobutane-1,2-dicarbonitrile Chemical compound N#CC1(Cl)CCC1(Cl)C#N MKEHNGFZTJTLBC-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- CZPLUOCTUPJSIZ-UHFFFAOYSA-N cyclobutane-1,2-dicarbonitrile Chemical compound N#CC1CCC1C#N CZPLUOCTUPJSIZ-UHFFFAOYSA-N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZBLACDIKXKCJGF-UHFFFAOYSA-N [2-(aminomethyl)cyclobutyl]methanamine Chemical compound NCC1CCC1CN ZBLACDIKXKCJGF-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005157 alkyl carboxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
Definitions
- the present invention is concerned with a process for the manufacture of ethylenes which are substituted in the l-position and have the general formula:
- R stands for either a hydrogen atom or a halogenatom, and R stands for a carboxylic acid group, an ester group or nitrile group or an aminomethyl'group, by thermal cleavage to cyclobutane compounds having corresponding substituents in the 1,2-position.
- cis-1,2-dimethylcyclobutane can be subjected to thermal cleavage under reduced pressure at a temperature of 380 to 430 0, resulting in the formation of cleavage products consisting partially of propylene and ethylene and a mixture comprising cis-2-butene and trans2-butene.
- the nature of the isolated cleavage products indicates that cis-1,2-dimethylcyclobutane is split at high temperatures in both the 1,2- and 3,4-linkages and in the 2,3- and 1,4-linkages.
- the present invention unexpectedly provides a process for making ethylenes substituted in the 1-position, wherein a compound having the general formula:
- R stands for either a hydrogen atom or a halogen atom and R stands for a carboxylic group, an ester group or a nitrile group, or in which R stands for a hydrogen atom and R stands for a CH -NH group
- R stands for either a hydrogen atom or a halogen atom and R stands for a carboxylic group, an ester group or a nitrile group, or in which R stands for a hydrogen atom and R stands for a CH -NH group
- R stands for a hydrogen atom and R stands for a CH -NH group
- R1 CH2 C/ R2 in which R stands for a hydrogen atom or a halogen atom and R stands for a carboxylic group, an ester group or a nitrile group, or R stands for a hydrogen atom and R stands for a -CH -NH group.
- the starting materials suitable for use in the process of the present invention include, for example: cyclobutane-1,2-dicarboxylic acid or 1,2dihalogeno-, e.g. 1,2-dichloroor 1,2-dibromo-cyclobutane-1,2-dicarboxylic acid, or the methyl-, ethyl, propyl or butyl ester of cyclobutane-1,2-dicarboxylic acid and the corresponding esters of 1,2-dihalogeno-, e.g.
- 1,Z-dihalogeno-cyclobutane compounds there may also be used l-halogeno-cyclobutane compounds, eg, l-halogeno-cyclobutane-1,2-dinitrile, 1- halogeno-cyclobutane-1,2-dicarboxylic acid and esters of l-halogeno-cyclobutane-1,2-dicarboxylic acid, the alcoholic components of which have 1 to 4 carbon atoms.
- chlorine or bromine derivatives of cyclobutane are used as the halogenated starting products.
- the above starting products are thermally split by being passed in vapor form through e.g. an electrically heated quartz tube, which is preferably maintained at a temperature of about 600 to 700 C. and under a pressure of preferably 5 to 20 mm. mercury.
- the vapors are allowed to remain in the reaction tube for a period of time of preferably about 0.5 to 2 seconds.
- the cleavage gas leaving the reaction tube should be cooled in a condenser at a temperature of about 20 to 30 C. and thereafter be liquefied and collected in a receiver cooled at a tempera ture of e.g. C.
- the liquefied cleavage product is distilled in conventional manner.
- the products prepared by the process of the present invention are mostly obtained in yields of more than They deserve special commercial interest because they are used inter alia as starting material for numerous syntheses and as monomers for use in polymerization and copolymerization processes.
- the small losses in yield are 3 not the result of a cleavage reaction other than in the 1,2- and 3,4-linkages, but are the customary result of the finishing treatment to which the products are ultimately subjected.
- Example 1 146 grams 1,2-dichloro-cyclobutane-1,2-dinitrile were 'caused to flow in vapor form at a pressure of 12 mm.
- Example 3 172 grams cyclobutane-1,2-dicarboxy1ic acid dimethylester, which had been obtained by hydrolyzing cyclobutane-LZdinitrile followed by esterification with methanol, were split in an electrically heated quartz tube at a pressure of 10 mm. mercury, a temperature of 600 C. and a time of residence of the material in the tube of 0.1 second. The resulting cleavage product and unreacted ester were separated by means of a condenser and collected in a receiver cooled at 70 C. The condensed reaction mixture was separated into its components by fractional distillation resulting in the formation of 72 grams acrylic acid methylester having a B.P. of 40-41 C. and of 93 grams unreacted ester. 45% of the cyclobutane-1,2-dicanboxylic acid dimethylester underwent conversion, and the acrylic acid methylester was obtained in a yield of 91.3%.
- Example 4 Cyclobutane-l,Z-dicarboxylic acid dibutylester, prepared by hydrolyzing cyclobutane-1,2-dinitrile followed by esterification with butanol, was split in a quartz tube at a pressure of 30 mm. mercury,.a temperature of 650 C. and a residence time of 0.1 second of the compound in the tube. Fractional distillation of the reaction mixture indicated a conversion rate of 78.4%, and acrylic acid butylester was obtained in a yield of 52.1% of the theoretical.
- Example 5 1 chloro cyclobutane-1,2-dicarboxylic dimethylester was split in the gaseous phase in a manner, analogous to that described in the preceding examples at 700 C., a pressure of mm. mercury and a time of residence of 0.11 second. The conversion rate was 92.1%. a-chloroacrylic acid methylester (B.P. :58 C.) and acrylic acid methylester were obtained in equal parts in a yield of 677.8% of the theoretical.
- Example 6 1,2-dichloro-cyclobutane-1,Z-dicarboxylic acid dimethylester was split under the conditions set forth in Example tuted in the 1-position, consisting essentially in passing a 4 5. The conversion rate was 88.4%, and a-chloro-acrylic acid methylester was obtained in a yield of 64% of the theoretical.
- Example 7 216 grams cyclobutane-1,2-dicarboxylic acid were caused to flow in vapor form at a pressure of 25 mm. mercury and at a temperature of 600 C. through an electrically heated quartz tube, and thermally split therein.
- the vapors were allowed to remain in the quartz tube for 0.13 second.
- the cleavage gases flowing oil were condensed and collected in a receiver cooled at -70 C..
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEK50201A DE1238899B (de) | 1963-07-12 | 1963-07-12 | Verfahren zur Herstellung von alpha-Halogenacryl-saeureestern oder -nitrilen |
| DEK50786A DE1230014B (de) | 1963-07-12 | 1963-09-10 | Verfahren zur Herstellung von primaerem Allylamin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3362983A true US3362983A (en) | 1968-01-09 |
Family
ID=25983753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US377413A Expired - Lifetime US3362983A (en) | 1963-07-12 | 1964-06-23 | Process for the manufacture of ethylenes substituted in the 1-position |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3362983A (de) |
| AT (1) | AT252198B (de) |
| BE (2) | BE650379A (de) |
| CH (1) | CH433250A (de) |
| DE (2) | DE1238899B (de) |
| GB (1) | GB1043305A (de) |
| NL (1) | NL142943B (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507902A (en) * | 1967-07-21 | 1970-04-21 | Standard Oil Co | Process for preparing alpha-chloroacrylonitriles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2773089A (en) * | 1954-10-29 | 1956-12-04 | Du Pont | Fluorinated olefinic nitriles |
| US3092654A (en) * | 1960-06-17 | 1963-06-04 | Du Pont | Preparation of dicarboxylic acid nitriles |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1317753A (de) * | 1963-05-08 | |||
| US2673875A (en) * | 1950-10-11 | 1954-03-30 | Gen Aniline & Film Corp | Dehydrohalogenation of dihalopropionic acid compounds |
| GB723547A (en) * | 1951-12-31 | 1955-02-09 | Distillers Co Yeast Ltd | Esters and nitriles of alphahaloacrylic acids |
| GB750638A (en) * | 1953-01-21 | 1956-06-20 | Gen Aniline & Film Corp | Dehydrochlorination of dichloropropionic acid compounds |
| GB813175A (en) * | 1954-08-06 | 1959-05-13 | Charles Herschmann | Process for the production of monohalogenated vinyl compounds from ª‡,ª‰-dihalogenated compounds |
| DE1030332B (de) * | 1955-11-09 | 1958-05-22 | Basf Ag | Verfahren zur Herstellung von ª‡-Chloracrylsaeureestern |
| DE1064502B (de) * | 1956-03-01 | 1959-09-03 | Basf Ag | Verfahren zur Herstellung von alpha-Chloracrylsaeureestern aus Dichlorpriopionsaeureern durch Chlorwasserstoffabspaltung |
| DE1024956B (de) * | 1956-03-01 | 1958-02-27 | Basf Ag | Verfahren zur Herstellung von ª‡-Chloracrylsaeureestern aus Dichlorpropionsaeureestern durch Chlorwasserstoffabspaltung |
| DE1021357B (de) * | 1956-03-01 | 1957-12-27 | Basf Ag | Verfahren zur Herstellung von ª‡-Chloracrylsaeureestern aus Dichlorpropionsaeureestern durch Chlorwasserstoffabspaltung |
| DE1076673B (de) * | 1956-03-01 | 1960-03-03 | Basf Ag | Verfahren zur Herstellung von ª‡-Chloracrylsaeureestern aus Dichlorpropionsaeureestern durch Chlorwasserstoffabspaltung |
| DE1030333B (de) * | 1956-05-08 | 1958-05-22 | Basf Ag | Verfahren zur Herstellung von ª‡-Chloracrylsaeureestern |
| US2870193A (en) * | 1957-03-15 | 1959-01-20 | Maxwell A Pollack | Making alpha-chloroacrylic compounds |
| DE1089754B (de) * | 1959-10-24 | 1960-09-29 | Knapsack Ag | Verfahren zur Herstellung von 1, 2-Dicyancyclobutan |
| DE1081008B (de) * | 1959-02-06 | 1960-05-05 | Knapsack Ag | Verfahren zur Herstellung von 1, 2-Dicyancyclobutan |
| DE1103330B (de) * | 1960-01-23 | 1961-03-30 | Knapsack Ag | Verfahren zur Herstellung von 1, 2-Dicyancyclobutan |
| DE1150381B (de) * | 1961-02-22 | 1963-06-20 | Muenzing & Comp Chem Fab | Verfahren zur Herstellung von ª-Chloracrylsaeurenitril durch Abspaltung von Chlorwasserstoff aus ª, ª-Dichlorpropionsaeurenitril |
-
0
- BE BE650455D patent/BE650455A/xx unknown
-
1963
- 1963-07-12 DE DEK50201A patent/DE1238899B/de active Pending
- 1963-09-10 DE DEK50786A patent/DE1230014B/de active Pending
-
1964
- 1964-06-16 CH CH779964A patent/CH433250A/de unknown
- 1964-06-23 US US377413A patent/US3362983A/en not_active Expired - Lifetime
- 1964-06-25 GB GB26325/64A patent/GB1043305A/en not_active Expired
- 1964-07-10 AT AT595564A patent/AT252198B/de active
- 1964-07-10 BE BE650379D patent/BE650379A/xx unknown
- 1964-07-10 NL NL646407892A patent/NL142943B/xx unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2773089A (en) * | 1954-10-29 | 1956-12-04 | Du Pont | Fluorinated olefinic nitriles |
| US3092654A (en) * | 1960-06-17 | 1963-06-04 | Du Pont | Preparation of dicarboxylic acid nitriles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507902A (en) * | 1967-07-21 | 1970-04-21 | Standard Oil Co | Process for preparing alpha-chloroacrylonitriles |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1238899B (de) | 1967-04-20 |
| GB1043305A (en) | 1966-09-21 |
| NL142943B (nl) | 1974-08-15 |
| CH433250A (de) | 1967-04-15 |
| BE650455A (de) | |
| AT252198B (de) | 1967-02-10 |
| NL6407892A (de) | 1965-01-13 |
| DE1230014B (de) | 1966-12-08 |
| BE650379A (de) | 1964-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ciganek | A ketenimine from the addition of a carbene to an isocyanide | |
| US2730543A (en) | Fluorinated nitriles | |
| US2862024A (en) | Fluorinated carbon compounds | |
| US2434606A (en) | Method of preparing succinonitrile | |
| SAUERS et al. | A new synthesis of β-cyanoesters | |
| US3755412A (en) | Alkylation of acetonitriles | |
| Drysdale et al. | A new synthesis of tropolone | |
| US3362983A (en) | Process for the manufacture of ethylenes substituted in the 1-position | |
| US2587210A (en) | Production of acrylamides | |
| US2417749A (en) | Preparation of olefinic nitriles by dehydration with acetic anhydride | |
| US2795601A (en) | Fluorinated 2-alkenoic acids, esters and amides | |
| US3234264A (en) | 1-cyano and 1-carbamoyl-3-alkylbicyclo [1.1.0] butanes and processes for preparing the same | |
| Rossi et al. | Stereospecific synthesis of (Z)-13-hexadecen-11-yn-1-yl acetate: The sex pheromone of the processionary moth, and of (5Z, 7E)-5, 7-dodecadien-1-ol, a sex pheromone component of the forest tent caterpillar | |
| US2231363A (en) | Preparation of alpha-chloracrylonitrile | |
| US3681438A (en) | Preparation of bicyclo (2.2.1) hept-2-en-ylmethyl acrylate | |
| US3280163A (en) | Production of mercapto-substituted nitriles | |
| Barney et al. | α, α-Difluoroglutaric Acid | |
| US2528708A (en) | Nitriles from isobutylene-nitrosyl chloride adduct | |
| US3115514A (en) | Process for preparing nitriles by pyrolysis of esters of cyanoformic acid | |
| US2150885A (en) | Addition products of saturated and unsaturated etiocholanones and their derivatives and a method of producing the same | |
| US1026691A (en) | Process of producing isoprene. | |
| US1541176A (en) | Process for the manufacture of styrol or its homologues | |
| US3322816A (en) | Process for preparing dicyanoacetylene | |
| US3318911A (en) | Method of preparing gamma-cyanobutyraldehyde acetals | |
| US3019265A (en) | Process for preparing irones |